腐植酸作用下γ-六氯环己烷在冰相中的光转化

doi:10.7503/cjcu20160414

摘要/Abstract

摘要：

研究了腐植酸(HA)存在下冰相体系中γ-六氯环己烷(γ-HCH)的光转化规律. 结果表明, HA浓度对γ-HCH的光转化率呈现低浓度促进而高浓度抑制的现象; 盐离子浓度、 N $O 2 -$ 及N $O 3 -$ 对γ-HCH的光转化率均有促进作用; 低浓度Fe³⁺对γ-HCH的光转化率有促进作用, 当Fe³⁺的浓度增大到50 μmol/L时, 呈现抑制效应; γ-HCH在不同pH值条件下光转化速率的大小顺序为碱性>中性>酸性. 冰相中HA通过产生单线态氧(¹O₂)、羟基自由基(·OH)及三重激发态(HA^*)加速γ-HCH的光转化. HA存在下γ-HCH的光转化产物主要是五氯环己烯、邻二氯苯和对二氯苯、一氯苯, 光转化过程中¹O₂通过消耗中间产物间接加速了γ-HCH的光转化过程.

关键词: γ-六氯环己烷, 腐植酸, 光转化, 冰

Abstract:

The photoconversion regularity of γ-hexachlorocyclohexane(γ-HCH) in snow and ice in the presence of humic acid(HA) were studied. The results showed that the photoconversion efficiency of γ-HCH was promoted at low initial concentration of HA, but inhibited at high concentration of HA. Salt ion concentration, N $O 2 -$ and N $O 3 -$ all promoted the photoconversion efficiency of γ-HCH. The photoconversion efficiency of γ-HCH was promoted at low initial concentration of Fe³⁺, but inhibited when the concentration of Fe³⁺ reached 50 μmol/L. The sequence of photoconversion rate of γ-HCH at different pH was alkaline>neutral>acidic. HA accelerated the photoconversion of γ-HCH by producing singlet oxygen(¹O₂), hydroxyl free radical(·OH) and triple excited state(HA^*) in ice. Photoproducts of γ-HCH in the presence of HA are mainly pentachloro-cyclohexene, p-dichlorobenzene and o-dichlorobenzene, 1-chlorobenzene, and ¹O₂ indirectly accelerated the photoconversion of γ-HCH by consuming the intermediate products.

Key words: γ-Hexachlorocyclohexane(γ-HCH), Humic acid(HA), Photoconversion, Ice

TrendMD:

包思琪, 康春莉, 钟宇博, 周林, 姚志富, 黄冬梅, 王宇寒, 田涛. 腐植酸作用下γ-六氯环己烷在冰相中的光转化. 高等学校化学学报, 2016, 37(12): 2253.

BAO Siqi, KANG Chunli, ZHONG Yubo, ZHOU Lin, YAO Zhifu, HUANG Dongmei, WANG Yuhan, TIAN Tao. Photoconversion of γ-Hexachlorocyclohexane in the Presence of Humic Acid in Ice^†. Chem. J. Chinese Universities, 2016, 37(12): 2253.

图/表 9

Fig.1 Conversion rate of γ-HCH in different concentration of humate in ice and water(cγ-HCH=60 μg/L)

Table 1 The first order kinetics equation and parameters of light conversion of γ-HCH

Reaction system	The first order kinetics equation	k/h^-1	t_1/2/h	Coefficient of determination, R²
Water phase	ln(c_t/c₀)=-0.0019t+3.9895	0.0019	364.74	0.9251
Ice phase	ln(c_t/c₀)=-0.0075t+0.0465	0.0075	92.40	0.9600

Fig.2 UV-Vis spectra of HA of different concentrationsc/(mg·L-1): a. 5; b. 8; c. 10; d. 15; e. 20.

Fig.3 Light conversion rate of γ-HCH at different pH values in icecγ-HCH=60 μg/L, cHA=10 mg/L. (A) cPBS=0.005 mol/L; (B) cPBS=0.05 mol/L.

Fig.4 Light conversion rate of γ-HCH with different concentrations of Fe3+ in icecγ-HCH=60 μg/L, cHA=10 mg/L.

Fig.5 Light conversion rate of γ-HCH with NO2- and NO3- in icecγ-HCH=60 μg/L; cHA=10 mg/L; cNO2-=5 mmol/L; cNO3-=5 mmol/L.

Fig.6 Light conversion rate of γ-HCH with different concentrations of NaN3 in icecγ-HCH=60 μg/L, cHA=10 mg/L.

Fig.7 Light conversion rate of γ-HCH with different concentrations of isopropanol in icecγ-HCH=60 μg/L, cHA=10 mg/L.

Scheme 1 Light conversion way of γ-HCH with HA in ice

参考文献 30

[1]	Kahan T. F., Kwamena N. O. A., Donaldson D. J., Atmos. Chem. Phys., 2010, 10(22), 10917—10922
[2]	Mcneill V. F., Grannas A. M., Abbatt J. P. D., Ammann M., Ariya P., Bartels-Rausch T., Domine F., Donaldson D. J., Guzman M. I., Heger D., Kahan T. F., Klan P., Masclin S., Toubin C., Voisin D., Atmos. Chem. Phys., 2012, 12(20), 9653—9678
[3]	Kahan T. F., Donaldson D. J., Environ. Sci. Technol., 2010, 44(10), 3819—3824
[4]	Kahan T. F., Donaldson D. J., J. Phys. Chem. A, 2007, 111(7), 1277—1285
[5]	Kahan T. F., Zhao R., Atmos. Chem. Phys., 2010, 10(2), 843—854
[6]	Kahan T. F., Zhao R., Jumaa K. B., Donaldson D. J., Environ. Sci. Technol., 2010, 44(4), 1302—1306
[7]	Grannas A. M., Bausch A. R., Mahanna K. M., J. Phys. Chem. A, 2007, 111(43), 11043—11049
[8]	O’concubhair R., Sodeau J. R., Acc. Chem. Res., 2013, 46(11), 2716—2724
[9]	Bartels-rsusch T., Jacobi H. W., Kahan T. F., Thomas J. L., Thomson E. S., Abbatt J. P. D., Ammann M., Blackford J. R., Bluhm H., Boxe C., Domine F., Frey M. M., Gladich I., Guzman M. I., Heger D., Huthwelker T., Klan P., Kuhs W. F., Kuo M. H., Maus S., Moussa S. G., McNeill V. F., Newberg J. T., Pettersson J. B. C., Roeselova M., Sodeau J. R., Atmos. Chem. Phys., 2014, 14(3), 1587—1633
[10]	Jonathan P. B., Cort A., Environmental Science: Processes and Impacts, 2014, 16(4), 748—756
[11]	Klan P., HoloubekI., Chemosphere, 2002, 46(8), 1201—1210
[12]	Bower J. P., Anastasio C., J. Phys. Chem. A, 2013, 117(30), 6612—6621
[13]	Takenaka N., Bandow H., J. Phys. Chem. A, 2007, 111(36), 8780—8786
[14]	Domine F., Bock J., Voisin D., Donaldson D. J., J. Phys. Chem. A, 2013, 117(23), 4733—4749
[15]	Ou X. X., Sun H. J., Wang C., Zhang F. J., Liu N., J. Henan Agr. Sci., 2012, 41(2), 18—20
	(欧晓霞, 孙红杰, 王崇, 张凤杰, 刘娜. 河南农业科学,2012, 41(2), 18—20)
[16]	Thomsen M., Lassen P., Dobel S., Hansen P. E., Carisen L., Moqensen B. B., Chemosphere, 2002, 49(10), 1327—1337
[17]	Zhao N., Lu Y. Z., Li G. J., Chem. Res. Chinese Universities, 2013, 29(6), 1180—1184
[18]	Xue H. H., Tang X. J., Kang C. L., Liu J., Shi L., Wang H. L., Yang T., Water Sci. Technol., 2013, 68(11), 2479—2484
[19]	Cho H., Shepson P. B., Barrie L. A., J. Phys. Chem. B, 2002, 106(43), 11226—11232
[20]	Xue H.H., The Photochemistry of Hexachlorocyclohexane in Water, Snow and Ice, Jilin University, Changchun, 2012
	(薛洪海. 六六六在水、冰和雪中的光化学行为, 长春: 吉林大学, 2012)
[21]	Yang D. M., Yuan J. M., Xia H., Environ. Prot. Chem. Ind., 2014, 34(1), 24—27
	(杨德敏, 袁建梅, 夏宏. 化工环保,2014, 34(1), 24—27)
[22]	Tang X. J., Wang Y. X., Kang C. L., Liu H. F., Chen B. Y., Qiu S. L., Chem. J. Chinese Universities, 2015, 36(9), 1719—1723
	(唐晓剑, 王依雪, 康春莉, 刘汉飞, 陈柏言, 裘式纶. 高等学校化学学报,2015, 36(9), 1719—1723)
[23]	Zhan M. J., Yang X., Xian Q. M., Kong L. R., Chemosphere, 2006, 63(3), 378—386
[24]	Ou X. X., Chen S., Quan X., Zhao H. M., Chemosphere, 2008, 72(6), 925—931
[25]	Wang F. L., Chen P., Su H. Y., Wang Y. F., Ma J. S., Yao K., Li F. H., Liu G. G., Lv W. Y., J. Environ. Sci. China, 2016, 36(8), 2859—2868
	(王枫亮, 陈平, 苏海英, 王盈霏, 马京帅, 姚琨, 李富华, 刘国光, 吕文英. 环境科学学报,2016, 36(8), 2859—2868)
[26]	Boxe C. S., Colussi A. J., Hoffmann M. R., Murphy J. G., Wooldridge P. J., Bertram T. H., Cohen R. C., J. Phys. Chem. A, 2005, 109(38), 8520—8525
[27]	He C., Photochemical Reactions of γ-HCH Under Simulated Sunlight in Ice Phase, Jilin University,Changchun, 2013
	(何冲. 模拟太阳光作用下冰相中γ-HCH的光化学反应, 长春: 吉林大学, 2013)
[28]	Bower J. P., Anastasio C., Atmos. Environ., 2013, 75, 188—195
[29]	Guo Z.X., Rose Bengal-sensitized Photodegradation of γ-Hexachlorocyclohexane in Ice, Jilin University, Changchun, 2013
	(郭志新. 玫瑰红作用下γ-HCH在冰相中的光敏化降解, 长春: 吉林大学, 2013)
[30]	Widchaya R., Araya T., Ratchaneekorn W., Chem. Res. Chinese Universities, 2014, 30(1), 149—156